Halogen Free

After a quick survey of a few of the technical service personnel in the office today, I put together a little snapshot of what is happening right now:

Amanda Hartnett and Ed Briggs are conferencing with an engineer that Amanda met at a local SMTA meeting.  This potential customer asked for product recommendations to improve their assembly process after they heard about Indium 8.9HF (a halogen free solder paste).

 


Brandon Judd is working on reducing voiding via profile modification with our flux coated preforms.

Mario Scalzo is tracking and organizing our technical team’s submissions to the Silver Quill program, where authors at Indium Corporation are recognized for technical papers and presentations.

Eric Bastow is helping a customer determine the best soldering materials for a medical application which involves soldering nitinol to nitinol. Common choices are using flux #2 or flux #3 with Indalloy 121 or Indalloy 182 – depending on the application.

And you’re reading what I’m doing right now. One interesting thing that I realized today is how we are working on very different things at the same time, both reactively and proactively. While some of us are fixing customer issues, others are helping to plan future processes to eliminate the need for a fix. 

Something that may not be apparent from this daily description is how this technical team works together. One of the nice things about being in the same office is that we can share ideas and learn from the experiences of our peers.  Even an office mate's tech call or brainstorm session can be a learning exercise. Working together gets us ready for your next call, so we can have the answer for you before it is even asked.

All the best
~Jim H

As a supplier of electronics materials, Indium Corporation is constantly faced with customer requests for “halogen-free” (HF) soldering fluxes and associated materials. This is an interesting trend, but we face several challenges here:

1/ What is “halogen-free”? We have not seen any consistent message from our customers on what they mean by a halogen-free flux. As a materials-supplier this is an absolute show-stopper.

Based on several conversations with interested parties, my understanding of the IPC status is as follows, and apologies for any misunderstandings to Tim Jensen (ICA) and Tom Newton (IPC). The IPC’s 4-33a Task Group, which was looking at a universal halogen-free material standard (J-STD-709), saw a failure of a second ballot on the standard, even when it got downgraded to a guideline. The 4-33a group faced numerous differences of opinion: on what materials should be included; what halogen levels are allowable; or even whether a single component could be considered a "homogeneous material” to be ground up and analyzed for halogens and so on. The task of defining HF will now reportedly be taken up by two separate groups from IPC and JEDEC.

Meanwhile, in March of this year, the Japanese organization JEITA quietly released their understanding (ET-7304) of what is meant by HF fluxes and solder pastes, using a 1000ppm halogen limit. This definition is clearly at odds with the IEC's definition of HF. That is, 900ppm by weight maximum of chlorine or bromine atoms, or a maximum of 1500ppm of both: the so-called “9-9-15” limit. .

2/ Which halogens? The strict definition of a Group VII element (halogen) is one of Fluorine (F), Chlorine (Cl), Bromine (Br), Iodine (I) and radioactive Astatine (At). From environmental reasons, chlorine and bromine in halogenated fire-retardant (HFR) materials that emit dioxins and similar compounds when heated should be eliminated. However, some customers are also throwing fluorine and iodine into this definition, too. This may be based on fears of electrical reliability, but from my perspective the customer is becoming defocused from the necessity of meeting environmental concerns.

3/ Does halogen = halogenated fire retardant? Not every halogen found in an electronic material is an indicator of a halogen-containing fire retardant!

Greenpeace is the main driver behind this, and I have, to date, been unable to get a response from them on how they will detect halogens on circuit boards. The fear from our customers, and our customers’ customers, is that an electronic device (iPhone / flat-screen TV or other) will be obtained by an environmental group; pulled apart; and X-ray fluorescence (XRF) used to detect halogens. The minimum sample size that can give a quantifiable result for halogen-free is reportedly 2grams: contrast this with the milligrams of material (residue) present from a no-clean flux in a cellphone, and you can see the issues in quantifying halogen levels based on flux residues. We can’t do it reliably.

4/ How can we confirm “zero” halogens? Contrast the JEITA standard with the requests from many customers for zero halogens / “no intentionally added” halogens / “elemental halogen-free” fluxes or some such. However, since many customers insist on third-party data-reporting, we are reliant on these analytical labs to reliably give us data. One of the challenges we face is when, for example, a lab reports “63ppm of chlorine”, based on a reported limit of detection (LOD) of 50ppm. Our customer is outraged: “You said it was halogen-free!”

Those of you familiar with the statistics of analytical chemistry will immediately see the two fallacies here: the first is that they have reported not the method detection limit (MDL), but the much-lower LOD. The MDL is a function of analytical equipment PLUS the errors in sample preparation and handling. The second fallacy is that you can not report 63ppm as a reliable, reproducible number, since the limit of quantitation (LOQ) – the limit at which you can actually give a figure for the concentration – is more than 3 x the MDL. The limit of analytical capability to reliably quantify the amount of halogen present is therefore around 150ppm or greater.

Instead of reporting “63ppm halogen”, a more accurate statement is: “In our single test, we found a small peak in our spectrum at the same elution time as a halide-ion. It may be a halogen, or it could be one of the millions of anionic organic species taht elute at the same retention time. The quantity found is well below the method detection limit, so we have no way of knowing if it is from contamination during the sample preparation, and we certainly can not tell how much is present.”

5/ What is a ‘homogeneous material”? Some customer standards require the level of halogen in a homogeneous material to be reported. We can probably safely say that a flux is a “homogeneous material”, but is a solder paste truly homogeneous? Both JEITA and Indium Corporation can agree that the flux-content needs to be the focus of the analysis, but an unscrupulous solder paste supplier may, for example, take the analysis of a 90%w/w metal solder paste, and report the results as “890ppm chlorine”, knowing that the level in the (10%) flux is 8,900ppm chlorine, essentially diluted by the 90% metal content.

Conclusion:

As a global electronics materials supplier, we at Indium Corporation can see three possible solutions to all these dilemmas:

a/ Adopt the JEITA specification – even though it goes against the 9-9-15 EIC recommendation. This allows us to be on a level footing with our Japanese competitors, but appears to put us at odds with the needs of some of the semiconductor assembly and electronics assembly industries.

b/ Adopt a three-tier specification based on the IPC/IEC recommendation – the Indium Corporation approach is given here (below).



Why three levels? Because our more discriminating customers are telling us that truly halogen-free fluxes are simply not as effective as those that contain small amounts of halogen. For those who are concerned about end product reliability, a “halogen-compliant” tier allows the best of both worlds.

c/ Report the atomic chlorine and bromine levels present in the flux component, and allow the customer to choose what they want, based on this.

If you are a user of Indium Corporation materials, or even a competitor of ours - what makes most sense here? Or is there a fourth or fifth way?

Chers! Andy

在Indium公司的主页www.indium.com , 有一个技术文章模块“New Technical Papers”。 如果你点击进入，就可以免费下载Indium公司的各种技术文章。

在这一周美国的SMTAI 2009展会上，Indium 公司一共主持6场技术文章演讲/研讨会， 还有Dr. Ron Lasky在开幕式上主讲对未来25年SMT行业的远景展望。 所以这些文章/演讲，都是围绕目前SMT行业中的三个热点/挑战：

•      微型化    Miniaturization 
•      无铅        Lead Free
•     无卤素    Halogen Free

Indium公司的技术文章以及和研讨会上的演讲，都将会和大家分享我们的研发/技术成果，以及我们是怎么样来迎接这些挑战的。

Enjoy & Cheers!  

Solder Basics...  If I needed to pick my favorite flux for hand soldering, it would easily be PoP Flux 030B.  I know it’s probably never going to find itself in household soldering toolkits, it’s a semiconductor packaging material – most people never need that good of a flux around the house, but I said it was my favorite, not the most practical. 

This is why PoP Flux 030B is the best choice around the house:

1) It has proven it’s solderability to ENIG, silver, oxidized copper, OSP, and nickel with Pb free and Sn/Pb alloys (which I’d choose any day for my personal soldering applications).

2) It is a halogen free, no-clean flux, so you can just leave it on the pipes, connectors, or stereo wires you’re connecting.

3) It is safe to use even if it isn’t completely heated and cured – this is rare for a no-clean flux.

4) The airless packaging process gives it a unique tack/viscosity ratio and a smooth texture that you just don’t get with cheapo off-the-store-shelf fluxes.

5) It activates at a relatively low temperature but can endure ~300degC reflow.  Hand soldering is not accurate, so I like the widened process window.

6) I think it’s pretty cool to use such an advanced flux for low-tech soldering, it’s overkill at its finest.

 This is a rare photo taken in the underground Structural Solder Joint Test Facility (SSJTF) nearly 5 miles below a small farming town in Central NY.  The light that you see is not really just a cellar window…

Got contacted last week by Tony Hilvers of the IPC (Association Connecting Electronics Industries). Tony tells me that the Canadian Government is considering banning some rosin and resin-based chemicals that may be of interest to flux formulators for both no-clean; solvent-clean; and even water-wash solder pastes and fluxes. The Canadians are at an early, investigative, stage here: allowing the various interested parties six months to respond.

My initial, knee-jerk reaction is as follows:

1/ While Tony and the IPC's rapid response is commendable, note that we in the electronics industry are not alone. Even a cursory Google search shows that the vast majority of these types of material are used in the following, multi-billion dollar, industries:

- Paper manufacturing

- Cosmetics

- Adhesives and glues

- Synthetic rubbers

- Coatings

- Printing inks and toners

We in the electronics industry are relatively small fry: combining our voice with that from these other industries, may give the Canadians pause for thought.

2/ If you're wondering why I'm so interested in this, it's simply because after the Pb-free switch in most of the Electronics Assembly industry, I am now seeing the Electronics Assembly and Outsourced Assembly and Test industries still in turmoil over the exact meaning of "halogen-free" solder fluxes. Industry sources are telling me that there is a strong movement to pull back from  the absolutist "zero tolerance for halogens of any kind" to a more rational call for a certain limit to them, based around the standard "9-9-15" halogen classification. The hard truth is that truly "no-intentionally-added" (NIA: that is, TOTALLY halogen-free) solder fluxes may, in some instances, simply not be as effective as those containing moderate amounts of halogens.. More on "halogen-free" in a couple of weeks.

3/ Eliminating rosins and rosin-derivatives, including materials that may be present in naturally-occurring rosin products, may not only have the beleagured Canadian timber industry up in arms, but will probably result in another protracted round of setting of allowable limits for "proscribed substances" some of which.... umm.... occur naturally.

All comments, corrections and clarifications gratefully received.

Cheers!  Andy

In many halogen-free discussions, the primary emphasis is on Bromine (Br) and Chlorine(Cl).  However, the halogens also include Fluorine(F), Iodine(I), and Astatine(At).  Most of us know several uses of F and I, but what is this element At?  

As it turns out, Astatine is is the rarest of all naturally occurring element.  According to Wikipedia, there is less than an ounce in the entire Earth's crust.  I think that means it is safe to assume we don't have to worry about it showing up in printed circuit boards!

Since At is extremely radioactive, I highly recommend avoiding it if you see some on the sidewalk but don't worry too much about it in your halogen-free testing.

Thin Film PV Cell

最近小忙，只能凑凑杂文，不好意思。

1． 先请教大家一个问题，在太阳能光伏薄膜技术(PV Thin Film Technology)中, 哪种技术在中国领先？爲什麽呢？ 太阳能光伏薄膜技术，主要有这几种：

• Amorphous Silicon (a-Si): 非晶硅
• CIGS: 铜铟镓硒(Copper Indium Gallium Selenium)
• CdTe: 碲化镉   

2. 关于公司裏的开会。 前天中午看牙医，他又准备给我嘴巴里面打麻醉针了。"怎么这次又打？我还以为这次的小治疗不需要了。怎么每次下午我要开会发言，都会遇上你的麻醉针？叫我等会怎么说话呀？"牙医问"会议很重要吗？"我郑重其事的回答"当然！无论和谁开会，每一个会议都是重要的。因为除了自己能给会议带来value之外，也是展现自己的机会，别人也会在心中评价你的…"牙医笑道"Such a corporate girl! Please be quiet for now."然后他毫不手軟一针下来，我这个talking-box (话匣子)也慢慢地少话了…Anyway, 在公司里面，对于每一个会议都认真对待，做好准备，應該沒錯的。下次我看牙医前要问清楚是否要打麻醉针了，不然很有可能会一边说话一边不自觉地流口水的。

3.  无卤化 (Halogen-Free): 明天开始会去美国西部休假10天。我知道自己会被那里的更纯净的自然景色给shock的，也更加会想起祖国（或是第三世界国家）在电子垃圾废墟中的人们(e-waste)…还是老话，今天，你无卤化了吗？   

Greenpeace continues to take unusual steps to push electronics companies to produce halogen-free products.  On Tuesday July 28th, Greenpeace activists climbed onto the roof of one of the HP buildings in Palo Alto to protest that HP is not moving fast enough to remove BFR's and PVC from their products.

It seems to me that HP is taking their time to figure out whether or not the alternatives are both safe, reliable, and cost effective.  It would make no sense to eliminate a hazardous material and replace it with something more hazardous.  The main reason for Greenpeace's protest is that Apple has already successfully eliminated virtually all of their use of BFR's and PVC.  However, the business model of HP and Apple are much different.  HP has to be very cost consious and has a much broader product range than Apple.  HP must be very careful in selecting alternatives that will work in all their products AND allow them to be competitive in the ultra-competitive computer market. 

 The humerous Dilbert cartoon reiterates an important fact about companies "going green."  While there are probably individual employees at the company who are passionate about helping the environment, the sole purpose of the company is to make money.  Companies use terms like "environmentally friendly," "reduced carbon footprint," and "green" to create a positive impression the the consumer which is designed to lead to more sales.

In many of the IPC Halogen-Free meetings, people would ask why go through such an undertaking.  Other people have asked  to wait for scientific methodologies for determining which halogens are actually bad.  Those questions ultimately don't matter.  The process is about developing a system that companies can refer to in order to make their claims of being better for the environment (and ultimately make more money).

Eliminating halogens may actually be better for the environment, but it is still too soon to tell.  We have no idea how good/bad the alternatives are.  Unfortunately, if switching to an unknown material allows the company to put a green sticker on it, then they don't have the incentive to carry out further testing on those alternatives.

If you are like me, when you hear the term "whammy" you think back to the 80's game show called Press Your Luck.  The electronics assembly industry is converging on what I like to call the triple whammy.  This would be very bad if you were playing Press Your Luck, but for us it is really the result of innovation and environmental movements.

The triple whammy in electronics is the convergence of two environmental (and legislative) movements combined with the continued advancement in electronics functionality.  Those three things are:

• Pb-Free: Many assemblers have already made this transition while others are just beginning this process.  Pb-Free alloys have higher melting points, poorer soldering characteristics, and, in some cases, decreased reliability.
• Halogen-Free: This transition is just beginning and has a dramatic impact on PCBs, cables, and soldering fluxes and pastes.
• Miniaturization: As the technology improves, we are putting more functionality into smaller devices.  This means that the PCB assembly process becomes much more challenging with tiny components and thin boards.

From an assembly perspective, the triple whammy means that we all need to focus being very diligent in selecting the best materials (PCB's, components, soldering materials) to do the job.  In addition, process optimization will have a dramatic effect on yields.

In the spirit of Press Your Luck, we need to use engineering and process expertise to ensure the whammies don't take us out of the game and we can all reap the "Big Bucks!"

Indium Corporation (I say "Indium Corporation": it's actually me and my colleague Tim Jensen) is in the middle of drafting a position statement on halogen-free electronics and semiconductor assembly materials. In talking to Tim, who is Indium's guru on all matters related to the drive towards halogen-free, we became rather confused by something that is missing in the debate.

We know that the current best method for preparing "halogens" in flux materials for quantitative analysis, is to convert the two different chemical types (ionic and covalent) to the ionic halide salts by using a so-called "oxygen bomb", whereby the material to be tested is placed in a metal chamber that is pressurized with oxygen and then heated. The residue in the chamber is then eluted with a known quantity of a halogen-free solvent (usually water), and analyzed. For the former boy scouts and girl guides amongst you, you will recall that burning a piece of wood leaves behind a lot of residual ash. Tim and I realized that there is something wrong with this if the material is a pure organic flux: which is a much simpler material than wood. For the non-chemists among you, this is the issue:

A standard organic flux material, as used in SMT, Semiconductor Assembly or Power Semiconductor Assembly, is a mixture of several different organic chamicals. It can be represented generically as:

C(a) H(b) N(c) O(d) Y(e), where C is carbon, H is hydrogen, N is nitrogen, O is oxygen and Y is a halogen (the usual ones of interest are chlorine, Cl, and bromine, Br). (a) to (e) are simple ratios.

If you then heat this in oxygen to the point of complete combustion (reaction with oxygen), the end products are therefore:

CO(2) , H(2)O, NO(2), residual oxygen gas (O(2) and .....some product from Y.

The assumption has always been that the Y will be a solid ionic halide, of form X(f)Y(g).

So what is "X" here, the metallic cation to balance the halide anion, "Y"? Whatdunnit? The simple answer is that it is probably a reaction with the inside of the metallic container, which is usually steel (so Cr or Fe or Ni could be correct). Other theories involving the acid formation (HY) are probably wrong, as the vapor pressure is too high. Theories about oxides of halogen also don't hold up to scrutiny, either because in YO(j), the Y halogen is in the wrong oxidation state (plus not minus) or they are unstable or a combination of both.

What do you think is going on here?

Cheers!

Andy

A lot has changed in the world of package-on-package in the last few years.  The most obvious change that I have seen is the development of specialized pastes for component dipping.  If you haven’t tried one of these pastes, here are 8 reasons why you should:

8)       More consistent transfer over time

7)       Head-in-pillow elimination

6)       Better wetting to a range of alloys

5)       Optimized metal loading

4)       Specially designed powder distribution

3)       Halogen-free flux formulations

2)       Maximized transfer volumes

1)       Higher possible yields

Team Indium: (LtoR) Mario Scalzo, Pat Ryan, Dana Ebensperger, Bill Manning, Greg Evans, Anita Brown and Ed Gudlauski

I would like to take a moment and talk about something that has nothing to do with Head-in-pillow defects, Halogen-free solder paste or Pb-Free solder reflow.

When I was in High School in 1993, an adorable little girl was abducted less than 3 miles from my home.  This was an outrageous crime in a sleepy little New York town!

To raise awareness of this heinous crime, a group of 7 courageous bicyclists rode to Washington DC to raise awareness and preach children's safety along the way, arriving in DC on May 25th, the first National Missing Children's Day.

12 years later, over 400 riders, like us on Indium's team, ride 100 miles every May to commemorate this ride and to raise funding for the National Center for Missing and Exploited Children, which works hand-in-hand with Law Enforcement to spread knowledge of and retrieval of missing kids.  We will always wear pink and blue in remembrance of that little girl, back in 1993 that was never found.

Our mission is "to make our children safer...one child at a time".  We have helped reunite 3000 of over 4600 missing children in 2008 with their parents and loved ones!

Donations are greatly appreciated and can be given on-line at Active.com/donate/RMFCCNY/MarioScalzo.  More information on our cause and our history can be found at RideForMissingChildren.com.

One of these chameleons was my former pet, the other was a fake model.  Interestingly, they are the same if you only ask certain questions about them.

·          Is it green?

·          Is it a lizard?

·          Does it have four legs?

The difference becomes apparent when you start asking the right questions

• Does it change color?
• What does it eat?
• Is it alive?

You must also ask the proper questions regarding halogen-free ball attach fluxes and flip-chip fluxes.

• How is it tested?
• What is the ppm level of Br, Cl, F?
• Does the material pass per j-std-709?

Make sure your getting the “Real Green”.

The question often arises as to whether or not a water wash solder paste should be halogen-free.  Since halogen-free is fundimentally an environmental issue, the key concern is all the materials that remain on the PCB when it is in the finished product.  Since the flux residue of a water wash solder paste needs to be cleaned after processing, there should be no residue remaining on the board.

I have also heard comments such as: "I need a halogen-free water wash solder paste because I don't want to risk halogen presence on the board if I don't end up properly cleaning it."   The issue here is that improperly cleaning a water wash paste is actually an electrical reliability issue (regardless of whether or not it contains halogens).  That residue remaining has a good chance of promoting corrosion and dendritic growth.  Making a halogen-free decision based on a lack of confidence in your process doesn't make sense to me!

This year we tried to plan something a little different for APEX.  Instead of the normal booth, we used the space as a meeting place for people to come and talk with other engineers (from Indium and other companies), charge their cell phone, and eat a healthy snack.  If you have been to any tradeshow in your life you'll understand – this was an oasis.

Many people that did not participate in APEX are asking what it was like, especially in light of the predicted drop in attendance.  We spoke with a few of the Indium members who made it out to Vegas this year to sum up APEX 2009:

Rick Short told us "…attendance was 25 to 30% lower than in 2008.  That said, the quality of the attendee was unusually high (KEY decision makers) and the number of really good leads that we captured was high.  We spent about 25% of what we spent in 2008 on the exhibit and did much better (leads)."

Dave Sbiroli mentioned "It's the same core group of industry experts that attend the show" in reference to the technical presentations and industry meetings.

Brandon Judd commented "Although we are in the middle of an economic downturn, there was definitely no lack of interest in Indium's solder products at this year's APEX EXPO in Las Vegas.  In fact, it was quite the contrary.  Several customers, both current and potential, approached our booth with new and exciting applications that show there just may be a light at the end of the tunnel for our industry."

Tim Jensen had this to say, "This year's APEX was probably the best in recent history.  While the attendance was down from last year, those who did attend came with a specific purpose: to educate themselves and solve their current issues.  At Indium Corporation, we were busy educating customers on the implications of going halogen-free and helping to address their current Pb-Free production challenges."

Pictured here is an FP-3082R turbocharger that is used on a Mitsubishi Eclipse.  In very general terms – a turbocharger helps small engines create the same amount of power as (or more than) a larger engine.  When correctly designed and applied, a turbocharged engine can be very efficient.

Although I don’t design flux, I notice the paradox that is involved with creating powerful halogen-free fluxes.  The halogens in fluxes made them more active, but now flux designers need to find other ways to formulate strong fluxes.  The new activators compensate for halogens in the way a turbocharger compensates for engine displacement.  Halogen-free fluxes can be as powerful as traditional halogen based fluxes, and they will probably obsolete many halogen containing fluxes in the future.

A recent interview with Andy Mackie,(Ph.D., Indium Corporation)in Advanced Packaging Magazine helped shed some light on where the semiconductor packaging industry is headed.  Key points of discussion include halogen-free, no-clean ball-attach fluxes, ultra-low residue power die-attach considerations.